CN109306243A - A kind of super hydrophobic coating and its preparation method and application of resistance to greasy dirt - Google Patents

A kind of super hydrophobic coating and its preparation method and application of resistance to greasy dirt Download PDF

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Publication number
CN109306243A
CN109306243A CN201810969504.2A CN201810969504A CN109306243A CN 109306243 A CN109306243 A CN 109306243A CN 201810969504 A CN201810969504 A CN 201810969504A CN 109306243 A CN109306243 A CN 109306243A
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nano
parts
silicon dioxide
titanium dioxide
modified
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Inventor
陆佳政
方针
胡建平
李波
王博闻
谢鹏康
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State Grid Corp of China SGCC
State Grid Hunan Electric Power Co Ltd
Disaster Prevention and Mitigation Center of State Grid Hunan Electric Power Co Ltd
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State Grid Corp of China SGCC
State Grid Hunan Electric Power Co Ltd
Disaster Prevention and Mitigation Center of State Grid Hunan Electric Power Co Ltd
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Priority to CN201810969504.2A priority Critical patent/CN109306243A/en
Publication of CN109306243A publication Critical patent/CN109306243A/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04Polysiloxanes
    • C09D183/08Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16Antifouling paints; Underwater paints
    • C09D5/1656Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662Synthetic film-forming substance
    • C09D5/1675Polyorganosiloxane-containing compositions
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16Antifouling paints; Underwater paints
    • C09D5/1687Use of special additives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2237Oxides; Hydroxides of metals of titanium
    • C08K2003/2241Titanium dioxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention discloses a kind of super hydrophobic coatings and its preparation method and application of resistance to greasy dirt, the coating includes the raw material of following parts by weight: 0.8-1.3 parts of terminal hydroxy group fluorosilicon oil, 0.02-0.1 parts of curing agent, 10-20 parts of tetrahydrofuran, 0.1-2 parts of silane coupler modified nano silicon dioxide sol, 0.03-0.6 parts of nano-titanium dioxide;Preparation method includes: that terminal hydroxy group fluorosilicon oil and curing agent are dissolved in tetrahydrofuran, and stirring adds modified silicon dioxide sol and nano-titanium dioxide, is stirred at room temperature to obtain the final product;The contact angle of gained coating is greater than 160 °, and resistance to greasy dirt is had excellent performance.The present invention passes through modified silicon dioxide sol and nano-titanium dioxide modified synergic, mould the multiple dimensioned coarse structure of coating surface, the greasy dirt in air is catalytically decomposed in nano-titanium dioxide, the hydrophobic performance of gained coating and resistance to greasy dirt are had excellent performance, comprehensive performance is good and stablizes, preparation method is simple, has a extensive future.

Description

A kind of super hydrophobic coating and its preparation method and application of resistance to greasy dirt
Technical field
The present invention relates to technical field of paint preparation, more particularly to a kind of super hydrophobic coating and its system of resistance to greasy dirt Preparation Method and application.
Background technique
Super-hydrophobic automatic cleaning surface, which refers to, is greater than 150 ° and surface of the roll angle less than 10 ° with the contact angle of water droplet, has The material of super hydrophobic surface has extensive practical application in industrial and agricultural production and daily life, such as preventing for glass surface Mist, the anti-icing of ultra-high-tension power transmission line, automatically cleaning construction material, the anti-corrosion of submerged structure and sail body, fabric it is antifouling and micro- Fluid transport etc..
In recent years, with the further investigation to super-hydrophobic coat, the preparation method of super-hydrophobic bionic coating emerges one after another, this Outside, it is unfolded about the research of the preparation method of super-hydrophobic coat mainly around following two points: is on the one hand how to mould solid table On the other hand the multiple dimensioned coarse structure in face is then how to reduce the surface energy of the surface of solids.
So far, existing due to many although there are many material system of super-hydrophobic bionic coating and preparation method The hydrophobicity of some super hydrophobic coatings, resistance to greasy dirt and generally not good enough in the adhesive force of substrate surface, and preparation process is complicated;This Outside, field operation experiences show the problems such as existing super hydrophobic coating is easily lost there is also bad mechanical property and hydrophobicity, comprehensive Performance needs to further increase.
In conclusion, by selecting suitable material system, improving preparation process how on existing Research foundation, mentioning For a kind of preparation method is simple, technique is controllable, hydrophobic performance low in cost, products obtained therefrom, resistance to greasy dirt performance, adhesive force, machine Tool intensity and the excellent super hydrophobic coating and preparation method thereof of weather resistance, have important theoretical and practical significance.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides super hydrophobic coating of a kind of resistance to greasy dirt and preparation method thereof and answer With.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
A kind of super hydrophobic coating of resistance to greasy dirt is provided according to an aspect of the present invention, the raw material including following parts by weight:
0.8-1.3 parts of terminal hydroxy group fluorosilicon oil, 0.02-0.1 parts of curing agent, 10-20 parts of tetrahydrofuran, improved silica is molten 0.1-2 parts of glue, 0.03-0.6 parts of nano-titanium dioxide.
Wherein, the molecular weight of the terminal hydroxy group fluorosilicon oil is 1000-100000, and the modified silicon dioxide sol is partial size The silane coupler modified nano silicon dioxide sol of 10-150nm, the partial size of the nano-titanium dioxide are 10-200nm.
In the above-mentioned technical solutions, the partial size of the modified silicon dioxide sol is 25-80nm.
Preferably, in the above-mentioned technical solutions, the solid content of the modified silicon dioxide sol is 5-50%.
Further, in the above-mentioned technical solutions, the solvent of the modified silicon dioxide sol is toluene, dimethylbenzene and first One of ethyl ketone.
Still further, in the above-mentioned technical solutions, the partial size of the nano-titanium dioxide is 20-120nm.
Further, in the above-mentioned technical solutions, the curing agent is methyltrimethoxysilane, methyl triethoxy Silane, n-octyl trimethoxy silane, n-hexyl trimethoxy silane, dodecyltrimethoxysilane, cetyl front three One of oxysilane and perfluoro decyl trimethoxy silane are a variety of.
In the above-mentioned technical solutions, the super hydrophobic coating includes the raw material of following parts by weight:
0.9-1.0 parts of terminal hydroxy group fluorosilicon oil, 0.08-0.1 parts of curing agent, 18-20 parts of tetrahydrofuran, improved silica is molten 1.6-1.8 parts of glue, 0.36-0.5 parts of nano-titanium dioxide.
Wherein, the molecular weight of the terminal hydroxy group fluorosilicon oil is 20000-75000, and the curing agent is perfluoro decyl trimethoxy Base silane or dodecyltrimethoxysilane, the modified silicon dioxide sol are solid content 25-32% and partial size 30-55nm Silane coupler modified nano silicon dioxide sol, the partial size of the nano-titanium dioxide is 25-55nm.
Further, in the above-mentioned technical solutions, the modified silicon dioxide sol the preparation method is as follows: with positive silicic acid Ethyl ester is silicon source, is added in methanol, and ammonium hydroxide is then added as catalyst, stirs evenly, the nanometer two of surface hydroxyl is made Silica sol;It is eventually adding silane coupling agent to be modified, obtains modified silicon dioxide sol.
A kind of preparation method of above-mentioned super hydrophobic coating is provided according to a further aspect of the invention, comprising:
S1, terminal hydroxy group fluorosilicon oil and curing agent are dissolved in tetrahydrofuran according to the ratio, obtained fluorine silicon rubber is stirred at room temperature Sol solution;
S2, modified silicon dioxide sol and nano-titanium dioxide be added to fluorine silicone rubber obtained in step S1 in proportion In solution, it is stirred at room temperature to obtain the final product.
In the above-mentioned technical solutions, in step S2, the mixing time is 90-150min.
Another aspect provides a kind of super-hydrophobic coating material of resistance to greasy dirt, the super-hydrophobic coating material according to the present invention It is made of above-mentioned super hydrophobic coating or above-mentioned coating, the coating is in polymeric substrate, glass baseplate and metal base table The adhesive force in face is respectively national standard zero level, level-one and level-one, and hydrophobic contact angle is greater than 160 °.
Advantages of the present invention:
(1) super hydrophobic coating of resistance to greasy dirt provided by the present invention using through silane coupler modified hydrophobicity by receiving Rice silicon dioxide gel and nano-titanium dioxide modified synergic fluorine silicone rubber, the hydrophobic performance of obtained coating is excellent, and property It can stablize, while have both good resistance to greasy dirt performance, ageing-resistant performance and mechanical performance, comprehensive performance and being substantially better than fluorine silicone rubber Coating;
(2) preparation method of the super hydrophobic coating of resistance to greasy dirt provided by the present invention passes through using through silane coupler modified Hydrophobic nano-silica colloidal sol and nano-titanium dioxide collaboration mould the multiple dimensioned coarse of super-hydrophobic coating material surface Structure substantially increases the hydrophobicity on coating material surface, further, since nano-titanium dioxide has photocatalysis performance, can urge Change the greasy dirt decomposed in air, to be conducive to the holding of coating material surface super-hydrophobic, in addition, nano-titanium dioxide table Face hydroxyl is more, may absorb water, and through silane coupler modified hydrophobic nano-silica colloidal sol then just can with gram This disadvantage is taken, by cooperateing with using through silane coupler modified hydrophobic nano-silica colloidal sol and nano-titanium dioxide Modified fluoro-silicone rubber coating materials, not only resistance to greasy dirt, and its super-hydrophobicity lasting stability, self-cleaning property are strong;
(3) preparation method of the super hydrophobic coating of resistance to greasy dirt provided by the present invention is simple, and technique is controllable, and required equipment is equal For common device, used raw material is easy to get and cheap, high production efficiency, is suitble to scale industrial production, and obtained Coating be suitable for a variety of substrates, the excellent combination property of the coating material coated has a extensive future, theoretical and practical It is significant.
Specific embodiment
Combined with specific embodiments below, specific embodiments of the present invention will be described in further detail.
Following embodiment is only used for further illustrating the contents of the present invention, should not be construed as limiting the invention.Not In the case where spirit of that invention and essence, to modifications or substitutions made by the method for the present invention, step or condition, this is belonged to The range of invention.
Unless otherwise specified, experiment reagent used in the embodiment of the present invention and material etc. are commercially available.
If not particularly pointing out, technological means used in the embodiment of the present invention is well known to the skilled person normal Rule means.
Embodiment 1
The embodiment of the invention provides a kind of super hydrophobic coating of resistance to greasy dirt, the raw material comprising following parts by weight:
It 1.2 parts of terminal hydroxy group fluorosilicon oil, 0.05 part of curing agent, 15 parts of tetrahydrofuran, 1.2 parts of modified silicon dioxide sol, receives 0.25 part of titanium dioxide of rice.
Specifically, the molecular weight of the terminal hydroxy group fluorosilicon oil is 1000-100000, and the curing agent is methyl trimethoxy oxygroup Silane, the modified silicon dioxide sol are the silane coupler modified nano silicon dioxide sol of partial size 10-150nm, institute The partial size for stating nano-titanium dioxide is 10-200nm.
The preparation method of the super hydrophobic coating of above-mentioned resistance to greasy dirt the following steps are included:
S1, terminal hydroxy group fluorosilicon oil, curing agent and tetrahydrofuran are weighed respectively according to the above ratio, and by terminal hydroxy group fluorosilicon oil and Curing agent is dissolved in tetrahydrofuran, under room temperature, stirs 50min, fluorine silicone rubber solution is made;
S2, modified silicon dioxide sol and nano-titanium dioxide are weighed respectively according to the above ratio, is added in step S1 and makes In the fluorine silicone rubber solution obtained, 90min is stirred at room temperature, the super hydrophobic coating of resistance to greasy dirt is made.
Embodiment 2
The embodiment of the invention provides a kind of super hydrophobic coating of resistance to greasy dirt, the raw material comprising following parts by weight:
0.96 part of terminal hydroxy group fluorosilicon oil, 0.09 part of curing agent, 18.5 parts of tetrahydrofuran, modified silicon dioxide sol 1.65 Part, 0.45 part of nano-titanium dioxide;
Wherein, the molecular weight of the terminal hydroxy group fluorosilicon oil is 20000-75000, and the curing agent is dodecyl trimethoxy Base silane, the modified silicon dioxide sol are solid content 30% and the silane coupler modified nanometer two of partial size 30-55nm Silica sol, the partial size of the nano-titanium dioxide are 25-55nm.
The preparation method of the super hydrophobic coating of above-mentioned resistance to greasy dirt the following steps are included:
S1, terminal hydroxy group fluorosilicon oil, curing agent and tetrahydrofuran are weighed respectively according to the above ratio, and by terminal hydroxy group fluorosilicon oil and Curing agent is dissolved in tetrahydrofuran, under room temperature, stirs 30min, fluorine silicone rubber solution is made;
S2, modified silicon dioxide sol and nano-titanium dioxide are weighed respectively according to the above ratio, is added in step S1 and makes In the fluorine silicone rubber solution obtained, 120min is stirred at room temperature, the super hydrophobic coating of resistance to greasy dirt is made.
Embodiment 3
The embodiment of the invention provides a kind of super hydrophobic coating of resistance to greasy dirt, the raw material comprising following parts by weight:
It 1.1 parts of terminal hydroxy group fluorosilicon oil, 0.08 part of curing agent, 16 parts of tetrahydrofuran, 1.4 parts of modified silicon dioxide sol, receives 0.3 part of titanium dioxide of rice.
Wherein, the molecular weight of the terminal hydroxy group fluorosilicon oil is 1000-100000, and the curing agent is perfluoro decyl trimethoxy Base silane, the modified silicon dioxide sol are solid content 40% and the silane coupler modified nanometer two of partial size 25-80nm Silica sol, the partial size of the nano-titanium dioxide are 20-120nm.
The preparation method of the super hydrophobic coating of above-mentioned resistance to greasy dirt the following steps are included:
S1, terminal hydroxy group fluorosilicon oil, curing agent and tetrahydrofuran are weighed respectively according to the above ratio, and by terminal hydroxy group fluorosilicon oil and Curing agent is dissolved in tetrahydrofuran, under room temperature, stirs 45min, fluorine silicone rubber solution is made;
S2, modified silicon dioxide sol and nano-titanium dioxide are weighed respectively according to the above ratio, is added in step S1 and makes In the fluorine silicone rubber solution obtained, 75min is stirred at room temperature, the super hydrophobic coating of resistance to greasy dirt is made.
Comparative example 1
Comparative example of the present invention provides a kind of coating, the raw material comprising following parts by weight:
0.96 part of terminal hydroxy group fluorosilicon oil, 0.09 part of curing agent, 18.5 parts of tetrahydrofuran.
Wherein, wherein the molecular weight of the terminal hydroxy group fluorosilicon oil is 20000-75000, and the curing agent is dodecyl Trimethoxy silane.
The preparation method of above-mentioned coating includes: to weigh terminal hydroxy group fluorosilicon oil, curing agent and tetrahydro furan respectively according to the above ratio Mutter, and terminal hydroxy group fluorosilicon oil and curing agent be dissolved in tetrahydrofuran, under room temperature, stir 30min to get.
Comparative example 2
Comparative example of the present invention provides a kind of hydrophobic coating, the raw material comprising following parts by weight:
1.1 parts of terminal hydroxy group fluorosilicon oil, 0.08 part of curing agent, 16 parts of tetrahydrofuran, 1.4 parts of modified silicon dioxide sol.
Wherein, the molecular weight of the terminal hydroxy group fluorosilicon oil is 1000-100000, and the curing agent is perfluoro decyl trimethoxy Base silane, the modified silicon dioxide sol are solid content 40% and the silane coupler modified nanometer two of partial size 25-80nm Silica sol.
The preparation method of above-mentioned coating the following steps are included:
S1, terminal hydroxy group fluorosilicon oil, curing agent and tetrahydrofuran are weighed respectively according to the above ratio, and by terminal hydroxy group fluorosilicon oil and Curing agent is dissolved in tetrahydrofuran, under room temperature, stirs 45min, fluorine silicone rubber solution is made;
S2, modified silicon dioxide sol is weighed according to the above ratio, be added in step S1 in fluorine silicone rubber solution obtained, Be stirred at room temperature 75min to get.
Comparative example 3
Comparative example of the present invention provides a kind of super hydrophobic coating of resistance to greasy dirt, the raw material comprising following parts by weight:
It 1.2 parts of terminal hydroxy group fluorosilicon oil, 0.05 part of curing agent, 15 parts of tetrahydrofuran, 2.4 parts of modified silicon dioxide sol, receives 0.75 part of titanium dioxide of rice.
Specifically, the molecular weight of the terminal hydroxy group fluorosilicon oil is 1000-100000, and the curing agent is methyl trimethoxy oxygroup Silane, the modified silicon dioxide sol are the silane coupler modified nano silicon dioxide sol of partial size 10-150nm, institute The partial size for stating nano-titanium dioxide is 10-200nm.
The preparation method of above-mentioned coating the following steps are included:
S1, terminal hydroxy group fluorosilicon oil, curing agent and tetrahydrofuran are weighed respectively according to the above ratio, and by terminal hydroxy group fluorosilicon oil and Curing agent is dissolved in tetrahydrofuran, under room temperature, stirs 50min, fluorine silicone rubber solution is made;
S2, modified silicon dioxide sol and nano-titanium dioxide are weighed respectively according to the above ratio, is added in step S1 and makes In the fluorine silicone rubber solution obtained, 90min is stirred at room temperature, the super hydrophobic coating of resistance to greasy dirt is made.
Meanwhile by applying coating made from the various embodiments described above and comparative example on different substrate, and test its performance.
Referring to standard GB/T/T 9286-1998 " frame of paint and varnish paint film is tested ", tested using cross-hatching Super-hydrophobic coating material is stated in glass plate, polycarbonate plate, polymethyl methacrylate plate, polyvinyl chloride panel, aluminium sheet, stainless steel The adhesive force of plate surface.
Referring to standard GB/T/T 6739-2006 " paint and varnish pencil method measures hardness of paint film ", super-hydrophobic painting is tested The pencil hardness of layer material.
Test water droplet super-hydrophobic coating material surface contact angle and coating material under 150 DEG C of high temperature aging 30 days Contact angle afterwards.
With oil pen after the scribing line of super-hydrophobic coating material surface, after oiliness person's handwriting is dry, is wiped with dry paper handkerchief, pass through oil The mark that property pen leaves judges its resistance to greasy dirt performance.
Test result is as follows shown in table 1.
The performance test results of prepared coating in 1 embodiment of the present invention of table and comparative example
Result in comparison in table can be seen that in comparative example 1, and adhesive force is preferable between coating and substrate, in terms of adhesive force It is suitable with the performance of embodiment 2, but due to there is no addition modified silicon dioxide sol and nano-titanium dioxide, coating surface not to have Multiple dimensioned coarse structure is formed, therefore contact angle on surface of coating is smaller, coating surface does not have super-hydrophobicity, in addition, inorganic The addition of nanoparticle can improve the hardness of coating to a certain extent.
In addition, adhesive force is preferable between coating and substrate in comparative example 2, it is suitable with 3 performance of embodiment in terms of adhesive force, by There is preferable compatibility between modified manometer silicon dioxide and fluorine silicone rubber, nano silica can be dispersed in fluorine silicon rubber well In glue, this can reduce the degree of roughness of coating surface to a certain extent, therefore contact angle on surface of coating is smaller, and coating surface is not With super-hydrophobicity.In addition, the not addition of nano-titanium dioxide, coating surface have just lacked the energy of photocatalysis Decomposition organic matter Power (i.e. the resistance to oil stains decrease of coating), in addition, the addition of nano silica can improve the hardness of coating to a certain extent.
The result of comparative analysis comparative example 3, it is found that since there is depositing for great amount of hydroxy group on nano-titania particle surface Nano-titanium dioxide is substantially hygroscopic, the super-hydrophobicity of coating surface can be made not hold using excessive nano-titanium dioxide (after i.e. coating and drop contact time have been grown, coating surface can gradually lose super-hydrophobicity) long;The use of nano-titanium dioxide Amount is very little, and coating surface can not mould fine multiple dimensioned coarse structure (i.e. super-hydrophobicity is not achieved in coating), and photocatalysis point Solve the ability decline (i.e. the resistance to greasy dirt performance decline of coating) of organic matter;The modified manometer silicon dioxide colloidal sol and nanometer of proper ratio The addition of the best performance of titanium dioxide modified synergic fluorine silicone rubber, inorganic nano-particle can improve the hard of coating to a certain extent Degree.
In summary it can be seen, preparation method provided by the embodiment of the present invention by using hydrophobic nano-silica and Nano-titanium dioxide modified synergic fluorine silicone rubber, the hydrophobic performance of obtained coating material is excellent, and performance is stablized, while simultaneous Have good resistance to oil stains, high temperature resistance, ageing-resistant performance and mechanical performance, comprehensive performance is substantially better than fluorine silicone rubber painting Material moulds the multiple dimensioned coarse of super-hydrophobic coating material surface using hydrophobic nano-silica and nano-titanium dioxide collaboration Structure substantially increases the adhesion property of coating material, in glass plate, polycarbonate plate, polymethyl methacrylate plate, polychlorostyrene A variety of substrate surfaces such as vinyl plate, aluminium sheet, stainless steel plate have good adhesive force, preferable hardness and excellent hydrophobic performance (150 ° of contact angle >) meets practical requirement, and under 150 DEG C of hot environments after aging 30 days, coating material still has There is super-hydrophobicity, therefore the super-hydrophobic coating material prepared has good high temperature resistant and ageing-resistant performance, long service life;Together When, since nano-titanium dioxide has photocatalysis performance, the greasy dirt in air can be catalytically decomposed, it is super to be conducive to super hydrophobic surface Hydrophobic holding.In addition, nano-titanium dioxide surface hydroxyl is more, may absorb water, and hydrophobic nano-silica is just This disadvantage can be overcome well.Utilize hydrophobic nano-silica and nano-titanium dioxide modified synergic fluorine silicone rubber coating material Material, not only resistance to greasy dirt, super-hydrophobicity lasting stability, self-cleaning property are strong.The method for preparing super-hydrophobic coat is suitable for industry Change and produce in enormous quantities, there is the powerful market competitiveness;Above-mentioned preparation method condition is simple, and technique is controllable, and required equipment is Common device, used raw material is easy to get and cheap, high production efficiency, is suitble to scale industrial production, and painting obtained Material is suitable for a variety of substrates, and the excellent combination property of the coating coated has a extensive future, theoretical and practical significance weight Greatly.
Finally, being not intended to limit the scope of the present invention the above is only preferred embodiment of the invention.It is all this Within the spirit and principle of invention, any modification, equivalent replacement, improvement and so on should be included in protection model of the invention Within enclosing.

Claims (10)

1. a kind of super hydrophobic coating of resistance to greasy dirt, which is characterized in that the raw material including following parts by weight:
0.8-1.3 parts of terminal hydroxy group fluorosilicon oil, 0.02-0.1 parts of curing agent, 10-20 parts of tetrahydrofuran, modified silicon dioxide sol 0.1-2 parts, 0.03-0.6 parts of nano-titanium dioxide;
Wherein, the molecular weight of the terminal hydroxy group fluorosilicon oil is 1000-100000, and the modified silicon dioxide sol is partial size 10- The silane coupler modified nano silicon dioxide sol of 150nm, the partial size of the nano-titanium dioxide are 10-200nm.
2. super hydrophobic coating according to claim 1, which is characterized in that
The partial size of the modified silicon dioxide sol is 25-80nm;
And/or the solid content of the modified silicon dioxide sol is 5-50%.
3. super hydrophobic coating according to claim 1 or 2, which is characterized in that the solvent of the modified silicon dioxide sol For one of toluene, dimethylbenzene and methyl ethyl ketone.
4. super hydrophobic coating according to claim 1-3, which is characterized in that the partial size of the nano-titanium dioxide For 20-120nm.
5. super hydrophobic coating according to claim 1-4, which is characterized in that the curing agent is methyl trimethoxy oxygen Base silane, methyltriethoxysilane, n-octyl trimethoxy silane, n-hexyl trimethoxy silane, dodecyl trimethoxy One of base silane, hexadecyl trimethoxy silane and perfluoro decyl trimethoxy silane are a variety of.
6. super hydrophobic coating according to claim 1, which is characterized in that the raw material including following parts by weight:
0.9-1.0 parts of terminal hydroxy group fluorosilicon oil, 0.08-0.1 parts of curing agent, 18-20 parts of tetrahydrofuran, modified silicon dioxide sol 1.6-1.8 part, 0.36-0.5 parts of nano-titanium dioxide;
Wherein, the molecular weight of the terminal hydroxy group fluorosilicon oil is 20000-75000, and the curing agent is perfluoro decyl trimethoxy silicon Alkane or dodecyltrimethoxysilane, the modified silicon dioxide sol are the silicon of solid content 25-32% and partial size 30-55nm The coupling agent modified nano silicon dioxide sol of alkane, the partial size of the nano-titanium dioxide are 25-55nm.
7. super hydrophobic coating according to claim 1-6, which is characterized in that the modified silicon dioxide sol The preparation method is as follows: being added in methanol using ethyl orthosilicate as silicon source, ammonium hydroxide is then added as catalyst, stirs evenly, makes Obtain the nano silicon dioxide sol of surface hydroxyl;It is eventually adding silane coupling agent to be modified, it is molten to obtain improved silica Glue.
8. a kind of preparation method of such as described in any item super hydrophobic coatings of claim 1-7 characterized by comprising
S1, terminal hydroxy group fluorosilicon oil and curing agent are dissolved in tetrahydrofuran according to the ratio, it is molten that obtained fluorine silicone rubber is stirred at room temperature Liquid;
S2, modified silicon dioxide sol and nano-titanium dioxide be added to fluorine silicone rubber solution obtained in step S1 in proportion In, it is stirred at room temperature to obtain the final product.
9. preparation method according to claim 8, which is characterized in that in step S2, the mixing time is 90- 150min。
10. a kind of super-hydrophobic coating material of resistance to greasy dirt, which is characterized in that use the described in any item coating of claim 1-8 Or preparation method as claimed in claim 9 is made, the coating is attached polymeric substrate, glass baseplate and metallic substrate surface Put forth effort respectively national standard zero level, level-one and level-one, hydrophobic contact angle is greater than 160 °.
CN201810969504.2A 2018-08-23 2018-08-23 A kind of super hydrophobic coating and its preparation method and application of resistance to greasy dirt Pending CN109306243A (en)

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CN112210293A (en) * 2020-10-16 2021-01-12 佛山市思特四通科技有限公司 Hydrophobic and oleophobic coating composition and preparation method thereof
CN113956074A (en) * 2021-10-28 2022-01-21 江苏钧瓷科技有限公司 Preparation method for improving voltage resistance of PTC (positive temperature coefficient) ceramic

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Application publication date: 20190205